Violet vat dyestuff of the 2-thionaphthene-2-indolindigo series



Patented June 7, 1927.

UNITED STATES PATENT OFFICE.

RICHARD HEBZ, OI TBANKIORT-ON-THE-IAIN, GERMANY, ASSIGNOB TO GRAB 8m. DYESTUFF CORPORATION, OF NEW YORK, N. Y., A CORPORATION 01' DELAWARE.

VIOLET VAT DYESTUFI OF THE 2-THION APH'1HENE-2-INDOLINDIGO SERIES.

80 Drawing. Application filed August li, 1928, Serial No. 127,473, and in Germany November 8, 1984.

The United States application Serial No. 87,676, filed on February 11th, 1926, relates to new violet vat dyestuffs of the 2-th1onaphthene-2-indolind1go series corresponding probably to the general formula:

3 e=-= \R B I \NH/ (1) (1) r arts of 4-methyl-5.7-dichl'orothene are suspended in about oxyt ionap 600 arts of 5.7- ichloro-a-isatinchloride in the same solvent is added, which latter solution may be prepared by heating 72 parts of 5.7-dichloroisatin with 72 parts of phosphorus pentachloride in 600 parts of chlorobenzene. The mixture is heated for some time at 60-70". The separated dyestuffs is filtered, washed and dri The new dyestufi, having probably the formula:

0 o o i\ (a? 0-0 s NH (1) 4s 1 l is, when dry, a reddish violet powder, soluble in concentrated sulfuric acid with a. eenish blue color, forming with alkaline ydrosulfite a yellow vat, from which cotton and wool is dyed pure bluish violet shades of an excellent fastness to washing,.

chlorine and light. Beside its excellent dyeing ro erties the dyestufi is particularly w pted for printing purposes.

chlorobenzene and a solution of- The above named 4-methyl-5.7-dichlorooxythionaphthene, melting in a pure state at about 135, may be obtained according to the general methods of production, as, for example, according to the method described in the application No. 87,676. An advane tageous process for its manufacture is the following: I

l-methyl 3 amino-4.6-dichlorobenzene is diazotized, the diazogroup is replaced by the xanthogen group accordin to Leuckhardts reaction, the xanthic acld ester thus formed is saponified to the corresponding mercaptan, and the latter is condensed with monochloroacet-ic acid, formin the l-methyl-4.6-dichlorophenyl 3 -thiog ycollic acid, melting in a pure state at about 106.

For the production of the 4-methyl-5.7- dichloro-oxythionaphthene this l-methyl- 4.6-dichlorophenyl-3-thioglycollic acid is either treated at low temperatures with suitable acid condensing agents, preferably with chlorosulfonic acid in the cold,'or the thioglycollic acid may be converted into the corresponding chloride for instance by heating it with phosphorus trichloride or thionylchloride andthe ring is then formed bymeans of suitable condensing agents, particularly by means of aluminiumchloride, phosphorus pentoxide etc.

This latter process has the advantage, that for the pro uction of the dyestuif the formed 4 methyl-5.7-dichlorooxythionaphthene need not be isolated.

One ma for instance, advantageously work as to lows: I

(b)- 8 parts of the above mentioned 1- methyl-4.6 dichlorobenzene 3 thio lycollic acid are mixed with 25 parts of chlorobenzene, then 10 (parts of phosphorus trichloride are added a the mixture is heated at about 115? for some hours. The conversion of the thioglycollic acid into its chloride is finishe when the whole mass is gone into solution. It is cooled-down to about 10 and 10 parts of anhydrous aluminium chloride are slowly ad ed. The condensation reaction takes place with an evolution of hydrochloric acid, and is completed by warmin the solution, at 40 for a short time. hen a solution of 8, 4 parts of 5.7-

dichloro-a-isatinchloride, prepared as described above, is allowed to run in while stirring. The formation of the dyestuffs of 5.7-dichloro-a-isatinchloride, a 5.7-dichloro-a-isatinarylide is used.

Similar dyestufis are formed when 0011; densing other a-isatinbodies, such as 5.7- dibromo-a-isatinchloride or arylide or a 6- chloro -7 -meth%l-a-isatinarylide with the aforesaid l-met yl-5.7-dichlorooxythionaphthene.

Example 2. If in Example 1 (a) the 4-methyl-5.7-dichlorooxythionaphthene is replaced by the corresponding amount of 4-methyl-5.6.7-tr1- chlorooxythionaphthene and otherwise is worked as described above, thena dyestufl is formed, having probably the formula:

01 o 0 o 0 c1 (3) a a C] s NH v which is verysimilar in its properties to the dyestuff, described in Example 1.

Also in this case instead of 5.7-dichloro-2- isatinchloride or -arylide 5.7-dibromo-a-isatinchloride or -arylide or other u-isatin bodies may be used. v i

The aforesaid 4-methyl-5.6.7-trichlorooxythionaphthene may be obtained according to the above described methods of production, starting from 1-methyl-3-amino-4.5.6-trichlorobenzene or it also advantageously may be roduced according to the rocesses descri ed in the British speci cations No. 17,417 of 1914 and No. 18,292 of 1914, starting from l-methyl-2-amino-4.6-dichloroor -4.5.6-trichlorobenzene.

Similar dyestuffs with the same excellent dyeing properties are obtained, if for instance -ethyl-5.7-dichlorooxythionaphthene or- 4.7 dimethyl-5-chlorooxyth-ionaphthene are condensed with 2-isatin-bodies.

I' claim:-

1.- As new com ounds violet vat dyestufl's of the 2-thionap thene-2-indolindigo series corfesponding probably to the general formu a:

. i 0- Y 6 7 s /m nn wherein X means a halogen or an alkylgroup, Y means hydrogen, which may be substituted by a halogen or an alkylgroup and R means an arylresidue, which may contain further substituents, which dyestuffs are, when dry, violet powders, soluble in concentrated sulfuric acid to a greenish, to blue solution, forming with alkaline hydrosulfite a yellowish vat, from which cotton v and wool is dyed in violet to bluish violet shades of an excellent fastness especially to washing, chlorine and light, whi h dyestuffs are substantially identical with the dyestufi's, obtainable by condensing oxythionaphthene derivatives, corresponding probably to the general formula:

wherein X means a halogen or an alkylgroup, Y means hydrogen which may be substituted by a halogen or an alkylgroup, with an oz-lSfit-lll body of the general formula:

corresponding probably to the general formula:

solution, forming with alkaline hydrosulfite a yellowish vat, om which cotton and wool are dyed in violet to bluish violet shades of an excellent fastness es ecially to washing,

chlorine and light, whic dyestufi's are substantially identical with the dyestufi's, obtainable by condensing oxythionaphthene derivatives, corresponding probably to the general formula:

s 6 hi Y 7 s wherein X means a halogen or an alkylgroup, Y means hydrogen, which may be substituted by a halogen or an alkylgroup, with an a-isatin body of the general formula:

wherein R means an arylresidue, which may contain further substituents, R means a halogen or an arylidogroup.

3. As'new compounds violet vat dyestuffs of the 2-thionaphthene-2-indolindigo series, corresponding probably to the formula:

alogen wherein Y means hydrogen which may be;

substituted by a halogen or an alkyl group; which are, when dry, reddish violet powders, soluble in concentrated sulfuric acid to a greenish blue solution, forming with alkaline hydrosulfite a yellow vat, from which cotton and wool is dyed pure bluish violet shades of an excellent fastness especially to* washing, chlorine and light; which dyestufis are substantially identical with the dyestufis obtainable by condensing 4-methyl-5.7-dichlorooxythionaphthene of the formula:

with an a-istin body of the formula:

Halogen Rg-O alogen wherein R means a halogen or an arylidogroup.

4. As new compounds violet vat dyestuffs of the 2-thionaphthene-2-indolindigo series corresponding probably to the formula:

Halogen Halogen which are, when dry, reddish violet powders, soluble in concentrated sulfuric acid to a greenish blue solution, forming with alkaline hydrosulfite a yellow vat, from which cotton and wool is dyed purebluish violet:

shades of an excellent fastness especially to washing, chlorine and light, which dyestuffs are substantially identical with the dyestufis, obtainable by condensing 4-methyl-5.6.7-tri- ,chlorooxythionaphthene of the formula:

with an u-isatin body of the formula:

oup. In testimony whereof, I affix my signature.

RICHARD HERZ. 

